Published on Web 09/24/2002
A Novel Layer-by-Layer Approach to Immobilization of
Polymers and Nanoclusters
Eugene W. L. Chan, Dong-Chan Lee, Man-Kit Ng, Guohui Wu, Ka Yee C. Lee, and
Luping Yu*
Contribution from the Department of Chemistry and The James Franck Institute,
The UniVersity of Chicago, 5735 South Ellis AVenue, Chicago, Illinois 60637
Received March 11, 2002
Abstract: This paper reports a simple method for the multilayer immobilization of conjugated polymers,
gold nanoparticles on solid supports. Poly(phenyenevinylene) functionalized with aldehyde and aminooxy
groups was chemoselectively immobilized onto both glass and gold substrates via layer-by-layer deposition.
The physical properties of the thin films were characterized by grazing angle IR, TM-AFM, fluorescence,
and UV-visible spectroscopy. This methodology was also successfully applied to prepare polymer/gold
nanocluster alternating multilayers. The results show that this methodology provides a general route for
preparing robust and functionalizable multilayer films on solid substrates with molecular-level thickness
control.
Introduction
the polymer side chains makes the coupling of multiple func-
tional groups onto the polymer surface difficult. New strategies
Surface immobilization of organic polymers on solid supports
to prepare nanostructured thin films has tremendous potential
applications in the areas ranging from light-emitting diode to
the coating for biomedical devices.1 Thin-film fabrication
approaches, including spin-coating, Langmuir-Blodgett tech-
niques, electrostatic adsorption of oppositely charged polyelec-
trolytes, and covalent attachment of polymers using conventional
coupling chemistry, have been previously demonstrated to
produce complex multilayer structures. The general utility of
these methods was further broadened when quantum dots and
for fabricating generally functionalizable and chemically stable
polymer films with well-defined thickness and surface func-
tionality would be very valuable for the preparation of novel
materials. In this paper, we introduce an efficient and effective
methodology for the preparation of these thin films based only
on the selective coupling of the reactive groups on the polymer
side chains. This approach simultaneously permits covalent
cross-linking of the polymer interlayer and chemical modifica-
tion of the polymer surface. The approach is based on the layer-
by-layer reaction between carbonyl compounds (ketones and
aldehydes) and alkyloxyamine, so-called chemoselective liga-
2
3
nanoparticles were being incorporated into the polymer matrix.
The versatility and complexity of these polymeric composites
provide new opportunities in the semiconductor, photovoltaic,
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tion.
As a demonstration of the general utility of this meth-
4
odology, we further apply this layer-by-layer reaction to
and molecular electronic fields. A number of reports in recent
literature, for example, have made nanoparticle composite thin-
film materials using layer-by-layer deposition of oppositely
charged polyelectrolytes. However, despite the ease of prepara-
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and hydrogen bonding. Furthermore, the lack of specificity of
*
To whom correspondence should be addressed. E-mail: lupingyu@
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midway.uchicago.edu.
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J. AM. CHEM. SOC. 2002, 124, 12238-12243
10.1021/ja026159o CCC: $22.00 © 2002 American Chemical Society